Phosphole and dishosphole ligands for catalysis

ABSTRACT

Novel reactions used to prepare phosphole and bisphosphole compounds are detailed. Novel phosphole compounds and metal coordination compounds of phosphole and bisphosphole compounds are also provided. These metal coordination compounds are useful as catalysts for the polymerization or olefins with carbon monoxide and for the polymerization of acrylic monomers.

FIELD OF INVENTION

[0001] The invention relates to new phosphole and diphosphole basedligands useful as polymerization catalysts.

BACKGROUND

[0002] The phosphole ring system is described by structure A. Thisstructure is distinct from the class of compounds B which contain benzorings fused to the phosphole core.

[0003] Class I has a much different electronic structure and thereforehas much different chemistry than compounds of class II. In class I, theP atom is part of the delocalized, partially aromatic ring system. Inclass II, the aromaticity is confined to the benzo rings, with nodelocalization around the P atom. Class I will participate inDiels-Alder chemistry (especially when complexed to a metal) (Bhaduri etal., Organometallics 1992, 11, pp. 4069-4076), whereas compounds ofclass II will not (Quin, Compr. Heterocycl. Chem. II Bird, Clive W (Ed),1996, Vol. 2, pp. 757-856).

[0004] Very few compounds have been reported that contain two phospholerings connected via a bridge (A) between the phosphorus atoms (structureC) (A=bridging hydrocarbon, hydrocarbon/heteroatom(s), or organometallicgroup).

[0005] One explanation for the paucity of compounds of type C-G is thelack of synthetic procedures broad enough in scope to prepare thephosphole ring system.

[0006] Examples reported in the literature include the compounds 1(Braye et al., Tetrahedron 1971, pp. 5523-37), 2 (A=—CH₂—, —CH₂CH₂—, and—CH═CH—CH═CH—) (Charrier et al., Organometallics 1987, 6 pp. 586 91),and 3 (Gradoz et al., J. Chem. Soc. Dalton Trans. 1992, pp. 3047-3051).

[0007] Compounds containing a single phosphole ring (I) were made usingthe Fagan-Nugent heterocycle synthesis (Fagan et al., J. Am. Chem. Soc.1994, 116, pp. 1880-1889; Fagan et al., J. Am. Chem. Soc. 1988, 110, pp.2310-2312). This synthesis involves preparing the zirconium reagents bycoupling of acetylenes followed by transfer of the metallacycle fromzirconium to phosphorus. In all cases, the substituent on the phosphoruswas an aromatic group such as phenyl.

[0008] These types of compounds (containing a single phosphole ring)have found limited utility as ligands for transition metals for use incatalysis, and have been shown to have different chemistries than theirphosphine analogs (Neibecker et al., New J. Chem. 1991, pp. 279-81;Neibecker et al., J. Mol. Catal. 1989, 57 pp. 153-163; Neibecker et al.,J. Mol Catal. 1989, 219-227; Vac et al., Inorg. Chem. 1989 28, pp.3831-3836; Hjortkjaer et al., J. Mol. Catal. 1989 50, 203-210).

[0009] Transition metal complexes have been made using structures ofclass VII, shown below, where the rings are linked at the position alphato phosphorus. Attempts to use these ligands to make Pd acetonitrilecomplexes analogous to those in the instant invention failed (Guoygou etal., Organometallics 1997, 16, 1008-1015).

[0010] Copolymers of carbon monoxide and olefins, such as ethylene, canbe made by free radical initiated copolymerization (Brubaker, J. Am.Chem. Soc., 1952, 74, 1509) or gamma-ray induced copolymerization(Steinberg, Polym. Eng. Sci., 1977, 17, 335). The copolymers producedwere random copolymers and their melting points were low. In 1951, Reppediscovered a nickel-catalyzed ethylene carbon monoxide copolymerizationsystem that gave alternating copolymers (U.S. Pat. No. 2,577,208(1951)). However, the molecular weights of these polymers were also low.

[0011] In 1984, U.S. Pat. Nos. 4,818,810 and 4,835,250 disclosed theproduction of alternating olefin carbon monoxide copolymers based onPd(II), Ni(II) and Co(II) complexes bearing bidentate ligands of theformula R₁R₂E-A-E-R₃R₄, wherein R₁, R₂, R₃, R₄, and A are organic groupsand E is phosphorus, arsenic, or antimony. When E is phosphorus and R₁₋₄are aryl groups, the corresponding diphosphine palladium complexes areactive in copolymerizing ethylene and carbon monoxide to producecopolymers of molecular weight up to 30,000 (MW_(n)) (Drent et al.,Chem. Rev., 1996, 96, 663). No compounds were claimed or disclosed inwhich R₁ and R₂, and R₃ and R₄ together formed a ring. Applicants haverecently found that the diphosphole coordinated palladium catalystscatalyze olefin/carbon monoxide (CO) copolymerization. When the P atomis part of a ring system, the electronic environment and thereforeexpected chemistries are different than simple, non-ring phosphinedisclosed in the patents described above.

[0012] Radical polymerization is an important commercial process formaking a variety of polymers of vinyl monomers, such as acrylics andstyrenics. While this process makes large amounts of polymers, thedifficulty in accurately controlling the polymer structures (such asmolecular weight, molecular weight distribution, and architecture, etc.)has significantly limited its further applications.

[0013] Living polymerization usually offers much better control onpolymer structures and architectures. While living polymerizationsystems for anionic, cationic, and group transfer mechanisms weredeveloped some years ago, a true living radical polymerization system isstill an elusive goal (because of the high reactivity of free radicals)and only very recently has pseudo-living radical polymerization beenachieved. One pseudo-living radical polymerization method is “atomtransfer radical polymerization” (ATRP). In this process a transitionmetal compound, usually in a lower valent state, is contacted with acompound which is capable of transferring an atom to the metal complex,thereby oxidizing the metal to a higher valent state and forming aradical which can initiate polymerization. However, the atom that wastransferred to the metal complex may be reversibly transferred back tothe growing polymer chain at any time. In this way, the propagation stepis regulated by this reversible atom transfer equilibrium andstatistically all polymer chains grow at the same rate. The results apseudo-living radical polymerization in which the molecular weight maybe closely controlled and the molecular weight distribution is narrow.

[0014] Such ATRPs are described in many publications (Kato et al.,Macromolecules 1995, 28, 1721; Wang et al., Macromolecules 1995, 28,7572; Wang et al., Macromolecules 1995, 28, 7901; Granel et al.,Macromolecules 1996, 29, 8576; Matyjaszewski et al., PCT WO 96/30421).The transition metal complexes used include complexes of Cu(I), Ru(II),Ni(II), Fe(II), and Rh(II). The complexes are formed by coordinating themetal ions with certain ligands such as nitrogen or phosphine containingligands. For Ru(II) and Fe(II), mono-phosphine P(C₆H₅)₃ was used as theligand. However, for Cu(I), all the ligands used are nitrogen-based suchas bipyridine or substituted bipyridine. No phosphine-based ligand hasbeen shown to be an effective ligand for Cu(I) in ATRP.

[0015] It has been found that novel types of ligands containingphosphole and other P ring systems can chelate Cu(I) to form activecatalysts for ATRP.

SUMMARY OF THE INVENTION

[0016] An object of this invention is to provide a process for thepreparation of compounds of formulae I and II

[0017] by reacting a compound of formula X₂P-A-PX₂ (III) with a compoundof formula IV;

[0018] wherein R₁, R₂, R₃ and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;R₂ and R₃ together can optionally form a ring; Cp is cyclopentadienyl; Xis selected from the group consisting of Cl, Br, and I; A is a divalentgroup consisting of optionally-substituted chains of from 1 to 12linear, branched, or cyclic carbons, optionally containing one or moreheteroatoms or organometallic groups in the chain, and —N(R₇)—N(R₈)—;and R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0019] Preferably A is selected from the group consisting of a carbonchain of 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl. More preferably R₁, R₂, R₃ andR₄ are alkyl groups.

[0020] The invention also provides for a compound of the formula

[0021] wherein R₁, R₂, R₃ and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S;R₂ and R₃ together and R₅ and R₆ together can optionally form a ring; Cpis cyclopentadienyl (η⁵—C₅H₅); A is a divalent group consisting ofoptionally-substituted chains of from 1 to 12 linear, branched, orcyclic carbons, optionally containing one or more heteroatoms ororganometallic groups in the chain, and —N(R₇)—N(R₈)—; and R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.

[0022] Preferably A is selected from the group consisting of a carbonchain of 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl. More preferably R₁, R₂, R₃ andR₄ are alkyl groups and R₅ and R₆ are selected from the group consistingof alkyl groups and Cl.

[0023] A further object of the invention is a coordination compoundcomprising one or more transition metals complexed to one or more of thefollowing compounds as ligands:

[0024] wherein R₁, R₂, R₃ and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S;R₂ and R₃ together and R₅ and R₆ together can optionally form a ring; Ais a divalent group consisting of optionally-substituted chains of from1 to 12 linear, branched, or cyclic carbons, optionally containing oneor more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0025] Preferably the transition metal is Pd and A is selected from thegroup consisting of a carbon chain of 1-3 carbons and —N(R₇)—N(R₈)—,wherein R₇ and R₈ are independently selected from the group consistingof hydrogen, hydrocarbyl, and substituted hydrocarbyl. More preferablyR₁, R₂, R₃, and R₄ are alkyl groups and R₅ and R₆ are selected from thegroup consisting of alkyl groups and Cl.

[0026] The invention also provides a process for the preparation of apolyketone by contacting a mixture of carbon monoxide with one or morealkenes under polymerization conditions with a catalyst comprising atransition metal complexed with one or more ligands of the formulae IIAor VA

[0027] wherein the rings are optionally-substituted and are optionallymembers of a larger bicyclic or tricyclic ring system; each P atom isbonded to only three other atoms in the ligand; the two atoms in thering adjacent to the P atom are C atoms; R₅ and R₆ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, Cl, Br, I, N, O, and S; R₅ and R₆ together can optionallyform a ring; A is a divalent group consisting of optionally-substitutedchains of from 1 to 12 linear, branched, or cyclic carbons, optionallycontaining one or more heteroatoms or organometallic groups in thechain, and —N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected fromthe group consisting of hydrogen, hydrocarbyl, and substitutedhydrocarbyl.

[0028] Preferably the transition metal is Pd and the ligand is of theformulae V or II

[0029] wherein R, R₂, R₃, and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S;R₂ and R₃ together and R₅ and R₆ together can optionally form a ring; Ais a divalent group consisting of optionally-substituted chains of from1 to 12 linear, branched, or cyclic carbons, optionally containing oneor more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. Morepreferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, R₇ and R₈ are independently selected fromthe group consisting of hydrogen, hydrocarbyl, and substitutedhydrocarbyl R₁, R₂, R₃, and R₄ are alkyl groups, R₅ and R₆ are selectedfrom the group consisting of alkyl groups and Cl, and the alkene isethylene.

[0030] Another object of the invention is a process for thepolymerization of an acrylic monomer by contacting at least one acrylicmonomer under polymerization conditions with a catalyst comprising Cu(I)complexed with one or more ligands of the formulae IIA or VA

[0031] wherein the rings are optionally-substituted and are optionallymembers of a larger bicyclic or tricyclic ring system; each P atom isbonded to only three other atoms in the ligand; the two atoms in thering adjacent to the P atom are C atoms; R₅ and R₆ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, Cl, Br, I, N, O, and S; R₅ and R₆ together can optionallyform a ring; A is a divalent group of optionally-substituted chains offrom 1 to 12 linear, branched, or cyclic carbons, optionally containingone or more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0032] Preferably the ligand is of the formulae V or II

[0033] wherein R₁, R₂, R₃, and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S;R₂ and R₃ together and R₅ and R₆ together can optionally form a ring; Ais a divalent group consisting of optionally-substituted chains of from1 to 12 linear, branched, or cyclic carbons, optionally containing oneor more heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. Morepreferably A is selected from the group consisting of a carbon chain of1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, andsubstituted hydrocarbyl, R₁, R₂, R₃, and R₄ re alkyl groups, R₅ and R₆are selected from the group consisting of alkyl groups and Cl, and theacrylic monomer is methylmethacrylate.

DETAILED DESCRIPTION OF THE INVENTION

[0034] This invention provides novel reactions used to prepare phospholeand bisphosphole compounds. Novel phosphole compounds and metalcoordination compounds of phosphole and bisphosphole compounds are alsoprovided. These metal coordination compounds are useful aspolymerization catalysts.

[0035] The present invention provides processes for the preparation ofbisphosphole compounds of formulae I and II

[0036] by reacting a compound of formula IV with a compound of formulaX₂P-A-PX₂ (III);

[0037] wherein:

[0038] R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;

[0039] R₂ and R₃ together can optionally form a ring;

[0040] Cp is cyclopentadienyl (η⁵—C₅H₅);

[0041] X is selected from the group consisting of Cl, Br, and I;

[0042] A is a divalent group consisting of optionally-substituted chainsof from 1 to 12 linear, branched, or cyclic carbons, optionallycontaining one or more heteroatoms or organometallic groups in thechain, and —N(R₇)—N(R₈)—; and

[0043] R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0044] By hydrocarbyl is meant a straight chain, branched or cyclicarrangement of carbon atoms connected by single, double, or triplecarbon to carbon bonds and/or by ether linkages, and substitutedaccordingly with hydrogen atoms. Such hydrocarbyl groups may bealiphatic and/or aromatic. Examples of hydrocarbyl groups includemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, cyclopropyl,cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl,methylcyclohexyl, benzyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl,vinyl, allyl, butenyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, andbutynyl. Examples of substituted hydrocarbyl groups include toluyl,chlorobenzyl, fluoroethyl, p-CH₃—S—C₆H₅, 2-methoxy-propyl, and(CH₃)₃SiCH₂.

[0045] “Coordination compound” refers to a compound formed by the unionof a metal ion (usually a transition metal) with a non-metallic ion ormolecule called a ligand or complexing agent.

[0046] Preferred compounds of formulae II and I include those where A isselected from the group consisting of —N(R₇)—N(R₈)— and carbon chains of1-3 carbons. Also preferred are compounds of formulae III and W whereR₁, R₂, R₃, and R₄ are alkyl groups. Most preferred are1,2-bis(2,3,4,5-tetramethylphospholyl)ethane;1,2-bis(2,3,4,5-tetraethylphospholyl)ethane;1,1-bis(2,3,4,5-tetramethylphospholyl)methane;1,1-bis(2,3,4,5-tetraethylphospholyl)methane;1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine;1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane; and1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine.

[0047] The process can be run in a wide variety of solvents. Preferredsolvents are CH₂Cl₂ and THF (tetrahydrofuran). Low temperatures, belowfrom about −100° C. to room temperature, are typically used.

[0048] The zirconium reagents (IV) are first prepared by reactingCp₂ZrCl₂ (Cp═η⁵—C₅H₅, cyclopentadienyl) with n-BuLi at about −78° C.followed by warming in the presence of an alkyne, alkynes, or dialkyne.The metallacycles can be isolated, or used in situ. When these arereacted with one-half of a molar equivalent of a diphosphorus compoundX₂P-A-PX₂, compounds of formula II result (Scheme 1).

[0049] If zirconium metallacycles of type IV are reacted with at leastone equivalent of the phosphorus reagents X₂P-A-PX₂, then compounds offormula I can be prepared (Scheme 2).

[0050] Dialkynes provide zirconium metallacycles of formula IVA whichcan be reacted with X₂P-A-PX₂ to form compounds of formula II wherein R₂and R₃ together form a ring as illustrated in Scheme 3.

[0051] where Z is any linking group with proper orientation or isflexible enough to allow the reaction to proceed. Examples of suitablelinking groups include hydrocarbyl, substituted hydrocarbyl, andorganometallic compounds. Preferred is —(CH₂)_(x)—, where X is 1-10.

[0052] The above reactions should be performed under a N₂ atmosphereusing anhydrous solvents.

[0053] Similarly, the products from reaction of zirconium metallacyclesIVA allows the corresponding compounds of formula I wherein R₂ and R₃together form a ring to be prepared (Scheme 4).

[0054] The present invention also provides for novel phospholecompositions of the formula V

[0055] wherein R₁, R₂, R₃, and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;

[0056] R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S;

[0057] R₂ and R₃ together and R₅ and R₆ together can optionally form aring;

[0058] A is a divalent group consisting of optionally-substituted chainsof from 1 to 12 linear, branched, or cyclic carbons, optionallycontaining one or more heteroatoms or organometallic groups in thechain, and —N(R₇)—N(R₈)—; and

[0059] R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0060] Preferred compounds of formulae V include those where A isselected from the group consisting of —N(R₇)—N(R₈)— and carbon chains of1-3 carbons. Also preferred are compounds of formulae V where R₁, R₂,R₃, and R₄ are alkyl groups, and where R₅ and R₆ are hydrocarbyl,substituted hydrocarbyl, alkoxy, Cl, Br, and I. Most preferred are1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine;[2-(tetramethylphospholyl)ethyl]-[(R,R)-2,7-dimethyl-3,6-decadiyl]phosphine;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methylphenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-chlorophenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-tert-butylphenyl)-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diethynylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-propynyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluorophenyl)phosphinoethane;1-(2,3,4,5-tetra-methylphospholyl)-2-di-(phenylethynyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-divinylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dicyclopentylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-decyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluoro-3-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-butylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-2-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-naphthyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methyl-thiophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-4-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-phenoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-[4-(dimethylamino)phenyl]phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4,6-trimethylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-isopropenylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diallyl-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-trimethylsilylmethyl-phosphinoethane;and1-(2,3,4,5-tetramethylphospholyl)-2-di-[2-[1,3]dioxan-2-yl-ethyl]phosphinoethane.

[0061] Compounds of formula V where X is Cl, Br, or I can be prepared asdetailed above. Other compounds of formula V can be prepared usingcompounds of formula I as an intermediate (Scheme 6).

[0062] wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, A, and Z are as definedabove, R₉ and R₁₀ are selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl;

[0063] M is any metal; and

[0064] R₂ and R₃ together and R₅ and R₆ together can optionally form aring.

[0065] An alternative route to compounds of formula V and othercompounds is the synthetic sequence shown in Scheme 7.

[0066] Alternate syntheses can be used to prepare bis(phosphole)compounds of formulae II from compounds previously detailed above(Scheme 8).

[0067] Another aspect of the present invention provides for novelcoordination compounds comprising one or more transition metalscomplexed to one or more compounds of formulae V or II

[0068] wherein R₁, R₂, R₃, and R₄ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl;

[0069] R₅ and R₆ are independently selected from the group consisting ofhydrogen, hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O and S;

[0070] R₂ and R₃ together and R₅ and R₆ together can optionally form aring;

[0071] A is a divalent group consisting of optionally-substituted chainsof from 1 to 12 linear, branched, or cyclic carbons, optionallycontaining one or more heteroatoms or organometallic groups in thechain, and —N(R₇)—N(R₈)—; and

[0072] R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.

[0073] The transition metals are hereby defined as metals of atomicweight 21 through 83. Preferred metals are those of Cu(I) or of PeriodicGroup VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.Most preferred is Pd.

[0074] Reactions to form coordination compounds use either awell-defined palladium catalyst such as [(diphosphole)PdMe(CH₃CN)]SbF₆or catalysts generated in situ by mixing the diphospole ligand withpalladium salts such as [Pd(CH₃CN)₄](BF₄)₂ or Pd(OAc)₂. Catalystsprepared in situ were made from1,2-bis(2,3,4,5-tetramethylphospholyl)ethane and Pd(OAc)₂ and from1,3-bis(2,3,4,5-tetraethylphospholyl)propane and [Pd(CH₃CN)₄(BF₄)₂.Preferred coordination compounds are[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMeCl;{[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]-PdMe(CH₃CN)} SbF₆;[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl;and {[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)} SbF₆.

[0075] Coordination compounds made in the instant invention can be usedas catalysts for olefin/carbon monoxide polymerizations. The olefin canbe an alkene or a cycloalkene containing 2-30, preferably 2-12, carbonatoms. Examples of suitable alkenes can include ethylene, propylene, anyisomeric butene, pentene, hexene, octene, and dodecene, cyclooctene,cyclododecene, styrene, methylstryene, acyrlic acid, methacrylic acid,alkyl esters of acrylic and metacylic acids, and dialkenes in which thetwo unsaturated groups are not conjugated.

[0076] Any suitable method to prepare polymer from carbon monoxide andan olefin using the instant catalysts can be used. The catalyststhemselves can be isolated before polymerization or generated in situ.Preferred catalysts for this process contain Pd.

[0077] The ligands made in the instant invention can also be used toprepare Cu(I) coordination compounds, which are useful as catalysts inATRP (atom transfer radical polymerization) processes, as defined above,to polymerize acrylic monomers. The acrylic monomers are of the formula

[0078] where R₁ is hydrogen, alkyl, or substituted alkyl group, and R₂is hydrogen, hydrocarbyl or substituted hydrocarbyl. Preferred arecompounds where R₁ is hydrogen, methyl or ethyl and R₂ is hydrogen ormethyl. Most preferred is where R₁ and R₂ are both methyl(methylmethacrylate).

[0079] Any suitable method to prepare the acrylic polymers using theinstant catalysts can be used. The catalysts themselves can be isolatedbefore polymerization or generated in situ. Preferred catalysts arethose formed in situ from 1,2-bis(2,3,4,5-tetramethylphospholyl)-ethaneand CuCl.

Materials and Methods

[0080] The following non-limiting Examples are meant to illustrate theinvention but are not intended to limit it in any way.

[0081] Abbreviations used hereafter are listed and defined below asfollows:

[0082] DSC—Differential scanning calorimetry

[0083] GPC—Gel Permeation chromatography

[0084] HFIP—1,1,1,3,3,3-Hexafluoroisopropanol

[0085] COD—1,5-Cyclooctadiene

[0086] FID—Flame ionization detection

[0087] ATRP—Atom transfer radical polymerization

[0088] MMA—Methyl methacrylate

[0089] ECO—Ethylene/carbon monoxide

[0090] All manipulations of air-sensitive materials were carried outwith rigorous exclusion of oxygen and moisture in flame-driedSchlenk-type glassware on a dual manifold Schlenk line, interfaced to ahigh-vacuum (10⁻⁴-10⁻⁵ Torr) line, or in a nitrogen-filled VacuumAtmospheres glovebox with a high-capacity recirculator (1-2 ppm of O₂).Before use, all solvents were distilled under dry nitrogen overappropriate drying agents (sodium benzophenone ketyl, metal hydridesexcept for chlorinated solvents). Deuterium oxide and chloroform-d werepurchased from Cambridge Isotopes (Andover, Mass.). All organic startingmaterials were purchased from Aldrich Chemical Co., Farchan LaboratoriesInc. (Kennett Square, Pa.), or Lancaster Synthesis Inc. (Windham, N.H.),and when appropriate were distilled prior to use. The substratezirconium metallacycle (η⁵—C₅H₅)₂ZrC₄Me₄,2,3,4,5-tetramethylphospholylchloride were synthesized according toliterature procedures. The substrates zirconium metallacycles(η⁵—C₅H₅)₂ZrC₄Et₄, (η⁵—C₅H₅)₂Zr(Me₃C—CCCH₂CH₂CH₂CC—CMe₃), and,2,3,4,5-tetraethylphos-pholylchloride, 1,7-ditertbutyl-1,6-bicyclo[3,3]heptadiynyl-phospholylchloride were synthesized viamodifications of literature methods as described below.

Physical and Analytical Measurements

[0091] NMR spectra were recorded on either a Nicolet NMC-300 wide-bore(FT, 300 MHz, ¹H; 75 MHz, ¹³C, 121 MHz ³¹P), or GE QM-300 narrow-bore(FT, 300 MHz, ¹H) instrument. Chemical shifts (δ) for ¹H, ¹³C arereferenced to internal solvent resonances and reported relative toSiMe₄. ³¹P NMR shifts are reported relative to external phosphoric acid.Analytical gas chromatography was performed on a Varian Model 3700 gaschromatograph with FID detectors and a Hewlett-Packard 3390A digitalrecorder/integrator using a 0.125 in. i.d. column with 3.8% w/w SE-30liquid phase on Chromosorb W support. GC/MS studies were conducted on aVG 70-250 SE instrument with 70 eV electron impact ionization. Meltingpoints and boiling points are uncorrected.

EXAMPLES

[0092] The following Examples are meant to illustrate embodiments of theinvention, but are not intended to limit its scope to the namedelements.

Example 1 Synthesis of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethaneMethod A

[0093] A solution of Cp₂ZrC₄Me₄ (2.76 g, 8.47 mmol) in CH₂Cl₂ (60 mL)was added dropwise to a stirring solution of1,2-bis(dichlorophosphino)ethane (0.97 g, 4.2 mmol) in CH₂Cl₂ (10 mL) atroom temperature over a period of 10 min, and the resulting reactionmixture was stirred for an additional 10 min before removal of thesolvent under vacuum. The residue was extracted with pentane (3×70 mL)and filtered. The filtrate was dried under vacuum, and then sublimatedat 130° C./10⁴ Torr to afford 1.0 g (78% yield) of(C₄Me₄P)CH₂CH₂(PC₄Me₄).

[0094]¹H NMR (300 MHz, CD₂Cl₂): δ 1.94 (s, 12H, 4Me), 1.91 (s, 12H,4Me), 1.33 (s, 4H, 2CH₂). ¹³C NMR (75 MHz, CD₂Cl₂): δ 143.8 (d, Jp-c=9.8Hz), 133.2 (s), 17.0 (d, Jp-c=23.0 Hz), 14.0 (s), 13.1 (d, Jp-c=21.8Hz). ³¹P NMR (122 MHz, CD₂Cl₂): δ 16.1 (s). Anal. Calcd for C₁₈H₂₈P₂: C,70.57; H, 9.21; P, 20.22. Found: C, 70.58; H, 9.02; P, 20.23.

Example 2 Method B

[0095] A mixture of Cp₂ZrCl₂ (27.0 g, 92.5 mmol) and 2-butyne (16.0 mL,204 mmol) in THF (150 mL) was treated dropwise with n-butyllithium (186mmol, 1.6 M solution in hexane) at −78° C. for 10 min. The resultingreaction suspension was then allowed to stir at room temperature for 2.5hr before cooling to 78° C. 1,2-bis(dichlorophosphino)ethane (10.7 g,46.3 mmol) was added, the mixture was warmed to room temperature andstirred for 30 min before removal of the solvent under vacuum. Theresidue was extracted with pentane (3×100 mL) and filtered. The filtratewas dried under vacuum, and then sublimated at 130,C/10⁴ Torr to afford9.9 g (70% yield) of(C₄Me₄P)CH₂CH₂(PC₄Me₄).

Example 3 Synthesis of 1,2-bis(2,3,4,5-tetraethylphospholyl)ethane

[0096] A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) above was usedin synthesis of the title compound yielding 5.0 g (92% yield).

[0097]¹H NMR (300 MHz, C₆D₆): δ 2.53 (m, 4H), 2.27 (m, 12H), 1.65 (t,J=5.7 Hz, 4H), 1.18 (t, J=7.2 Hz, 12H), 0.99 (t, J=7.5 Hz, 12H). ¹³C NMR(75 MHz, C₆D₆): δ 148.7, 142.1, 22.0 (d, Jp-c=19.4 Hz), 21.0, 17.8 (d,Jp-c=25.5 Hz), 17.1 (d, Jp-c=8.5 Hz), 15.4. ³¹P NMR (122 MHz, C₆D₆): δ 4(s). MS (rel. abundance): M⁺(33), M⁺−Me(60), M⁺−Et(15), 223.2(6),195.1(26), 167.1(14). High-resolution mass spectrum: Calcd for C₂₆H₄₄P₂(M⁺): 418.2918. Found: 418.2924. Anal. Calcd for C₂₆H₄₄P₂: C, 70.57; H,9.21; P, 20.22. Found: C, 74.14; H, 10.70; P, XX.

Example 4

[0098] The procedure was the same as described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method B). The product,(C₄Et₄P)CH₂CH₂(PC₄Et₄), was isolated in 65% yield.

Example 5 Synthesis of1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine

[0099] A solution of Cp₂ZrCl₂ (6.67 g, 20.0 mmol) and Cl₂PN(Me)N(Me)PCl₂(2.3 g, 8.6 mmol) in CH₂Cl₂ (150 mL) was refluxed overnight beforeremoval of the solvent. The resulting residue was extracted with 3×100mL of hexane. After removal of the hexane, the residue was sublimated at170° C./10⁻⁵ Torr, and then recrystallized from hexane to afford 2.67 g(92% yield) of title compound.

[0100]¹H NMR (300 MHz, CD₂Cl₂): δ 2.60 (d, JP-H=3.9 Hz, 6H, 2Me-N), 2.00(d, JP-H=9.9 Hz, 12H, 4Me), 1.84 (d, JP-H=2.7 Hz, 12H, 4Me). ¹³C NMR (75MHz, CD₂Cl₂): δ 140.2 (d, Jp-c=15.9 Hz), 132.4 (s), 39.4 (s), 13.1 (s),12.8 (d, Jp-c=3.6 Hz). ³¹P NMR (122 MHz, CD₂Cl₂): δ 77.2 (s). MS (rel.abundance): M⁺(61), M⁺−Me(2), 278.1(15), 197.1(31), 168.1(100),139.1(62). High-resolution mass spectrum: Calcd for Cl₈H₃₀N₂P₂ (M⁺):336.1884. Found: 336.1881.

Example 6 Synthesis of 1,1-bis(2,3,4,5-tetramethylphospholyl)methane

[0101] A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) was used insynthesis of the title compound yielding 1.30 g (97% yield).

[0102]¹H NMR (300 MHz, C₆D₆): δ 2.06 (m, 14H), 1.74 (s, 12H). ¹³C NMR(125.7 MHz, C₆D₆): δ 142.8, 136.7, 19.3 (t, Jp-c=31.9 Hz), 14.1, 14.0(t, Jp-c=12.9 Hz). ³¹P NMR (122 MHz, C₆D₆): δ 4.3. MS (rel. abundance):M⁺(96), M⁺+H(100), M⁺−H(30), 153(54). High-resolution mass spectrum:Calcd for C₁₇H₂₆P₂ (M⁺): 292.1510. Found: 292.1513.

Example 7 Synthesis of 1,1-bis(2,3,4,5-tetraethylphospholyl)methane

[0103] A procedure similar to that described above for1,2-bis(2,3,4,5-tetra-methylphospholyl)ethane (Method A) above was usedin synthesis of the title compound (1.70 g, 92% yield).

[0104]¹H NMR (300 MHz, C₆D₆): δ 1.02 (t, J=7.6 Hz, 12H), 1.25 (t, J=7.5Hz, 12H), 2.29 (m, 8H), 2.56 (m, 10H). ¹³C NMR (125.7 MHz, C₆D₆): δ149.0, 147.5, 23.8 (t, Jp-c=10.8 Hz), 22.7, 19.5, 17.1. ³¹P NMR (122MHz, C₆D₆): δ 8.1. MS(rel.abundance): M⁺(33),M⁺−H(7),M⁺−Me(7),M⁺−Et(17),209.1(100), 195.1(22), 181.1(19), 167.198). High-resolution massspectrum: Calcd for C₂₅H₄₂P₂ (M⁺): 404.2762. Found: 404.2777.

Example 8 Synthesis of1-(2,3,4,5-tetramethylphospholvl)-2-dichlorophospinoethane

[0105] A solution of Cl₂PCH₂CH₂PCl₂ (4.0 g, 16.9 mmol) in CH₂Cl₂ (70 mL)was treated dropwise with a solution of Cp₂ZrC₄Me₄ (5.6 g, 16.9 mmol) inCH₂Cl₂ (50 mL) at −39° C. over a period of 3 hr. The resulting reactionmixture was then slowly warmed to room temperature and stirred overnightbefore removal of the solvent. The residues were extracted with hexane(3×100 mL) and the extracts were concentrated to give 4.1 g (90% yield)of colorless oil.

[0106]¹H NMR (300 MHz, C₆D₆): δ 1.90 (m, 2H), 1.79 (d, J=10.5 Hz, 6H),1.63 (s, 6H), 1.59 (m, 2H). ¹³C NMR (75 MHz, C₆D₆): δ 144.8, 133.0, 37.7(d, Jp-c=48.8 Hz), 15.2 (dd, J=9.8 Hz), 13.9, 13.0 (d, J=22.0 Hz). ³¹PNMR (122 MHz, C₆D₆): δ 197.7, 11.4. MS (rel. abundance): M⁺(18),232.0(100), 204.0(30), 138.0(82), 123.0(40), 91.1(26). High-resolutionmass spectrum: Calcd for C₁₀H₁₆Cl₂P₂ (M⁺): 268.0104. Found: 268.0101.

Example 9 Synthesis of1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophospino-1,2-dimethylhydrazine

[0107] A procedure analogous to that described above for1-(2,3,4,5-tetra-methylphospholyl)-2-dichlorophospinoethane was used inthe synthesis of this diphosphine derivative with Cp₂ZrC₄Me₄ (6.2 g,18.78 mmol) and Cl₂PN(Me)N(Me)PCl₂ (5.0 g, 18.7 mmol) at roomtemperature. The NMR yield (˜90%) was estimated by the ¹H and ³¹P NMR.

[0108]¹H NMR (300 MHz, CD₂Cl₂): δ 3.07 (d, JP-H=5.1 Hz, 3H, Me-NPCl₂),2.65 (dd, JP-H=1.5 Hz, 3H, MeNNPCl₂), 2.00 (d, JP-H=10.5 Hz, 6H, 2Me),1.85 (d, JP-H=3.3 Hz, 6H, 2Me). ¹³C NMR (75 MHz, CD₂Cl₂): δ 143.4 (d,Jp-c=16.9 Hz), 131.2 (s), 39.7 (s), 33.7 (d, Jp-c=6.1 Hz), 13.9 (d,Jp-c=2.4 Hz), 13.0 (d, Jp-c=21.8 Hz). ³¹P NMR (122 MHz, CD₂Cl₂): δ 153.3(d, Jp-p=12.8 Hz), 82.9 (d, Jp-p=14.9 Hz). MS (rel. abundance):M⁺−HCl(24), 227.1(29), 196.0(20), 167.1(90), 137.0(94), 60.0(100),232.0(100), 204.0(30), 138.0(82), 123.0(40), 91.1(26). High-resolutionmass spectrum: Calcd for C₁₀H₁₇N₂P₂Cl (M⁺−HCl): 262.0556. Found:262.0558.

Example 10 Synthesis of 1,3-bis(2,3,4,5-tetraethylphospholyl)propane

[0109]

Synthesis of (2,3,4.5-tetramethylphospholyl)lithium

[0110] To a solution of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethaneprepared as described in Example 1, Method A, 5.0 g (16.3 mmol) in THF(70 mL) at room temperature was added clean Li ribbon (1.0 g, 144.0mmol) under Ar. The reaction mixture was allowed to stir overnightbefore filtering out the excess Li. The filtrate was dried in vacuum toafford 4.7 g (99% yield) of title compound. Reduction of theethano-bridged diphosphole ligand resulted in removal of the bridge(presumably as ethylene) and formation of the tetramethylphospholylanion. The NMR data agree with literature data (Douglas et al., 1989,Angew. Chem. Int. Ed. Engl. 28 (10), 1367-7.)

Synthesis of (2,3,4,5-tetraethylphospholyl)lithium

[0111] A procedure similar to that for(2,3,4,5-tetramethylphospholyl)lithium described above was used insynthesis of the title compound using1,1-bis(2,3,4,5-tetraethylphospholyl)methane from Example 7 as thestarting material (1.23 g, 98% yield).

[0112]¹H NMR (300 MHz, THF-d₈): δ 2.54 (t, J=7.9 Hz, 4H), 2.37 (d, J=7.2Hz, 4H), 1.14 (m, 6H), 0.96 (m, 6H). ³¹P NMR (122 MHz, THF-d₈): δ 56.0.

[0113] A suspension of Li C₄Et₄P (1.75 g, 8.67 mmol) in THF (80 mL) wastreated dropwise with BrCH₂CH₂CH₂Br (0.88 g, 4.34 mmol) at −30° C. for10 min. The resulting reaction mixture was then warmed to roomtemperature and refluxed overnight. The solution was cooled to roomtemperature and quenched with CH₃OH (3.0 mL). After removal of thesolvents, the residue was extracted with 3×50 mL of hexane. The combinedhexane extracts were dried under reduced pressure to give 0.81 g (44%yield) of (C₄Et₄P)CH₂CH₂CH₂(PC₄Et₄).

[0114]¹H NMR (300 MHz, C₆D₆): δ 2.50 (m, 4H), 2.25 (m, 14H), 1.68 (m,4H), 1.19 (t, J=7.2 Hz, 12H), 0.99 (t, J=7.2 Hz, 12H). ¹³C NMR (75 MHz,C₆D₆): δ 147.9, 142.9, 25.4 (d, Jp-c=17.1 Hz), 22.0 (d, Jp-c=18.3 Hz),21.5, 21.1, 17.4, 15.6. ³¹P NMR (122 MHz, C₆D₆): δ 2.38. MS (rel.abundance): M⁺(17), M⁺−Et(100), 237.2(60). High resolution massspectrum: Calcd for C₂₇H₄₆P₂ (M⁺): 432.3075. Found: 432.3094.

Examples 11-40 Reaction With Grignards

[0115]

[0116] A set of twenty-eight 5 ml vials were charged with 0.25 mmol eachof the following Grignards (Table 1) and 1.0 ml solution of 3 (0.1 mmol)in THF. The reactions were shaken overnight, and solvent was removed invacuo. Samples were checked by mass spectroscopy (Atmospheric PressureChemical Ionization) for the presence of the expected product. In allcases, the product was observed. TABLE 1 m/e + 1 m/e + 1 ExampleGrignard Concentration Formula expected found 11 p-CH₃—C₆H₄MgBr 10M/Ether C₂₄H₃₀P₂ 381.18 381.27 12 p-Cl—C₆H₄MgBr 1.0 M/Ether C₂₂H₂₄P₂Cl₂421.07 421.19 13 p-(CH₃)₃C—C₆H₄MgBr 2.0 M/Ether C₃₀H₄₂P₂ 465.28 465.3 14H—C≡C—MgBr 0.5 M/THF C₁₄H₁₈P₂ 249.08 249.15 15 CH₃C≡CMgBr 0.5 M/THFC₁₆H₂₂P₂ 277.11 277.2 16 p-F—C₆H₄MgBr 2.0 M/Ether C₂₂H₂₄P₂F₂ 389.13389.23 17 C₆H₅C≡CMgBr 10 M/THF C₂₆H₂₆P₂ 401.15 401.27 18 CH₂═CHMgBr 1.0M/THF C₁₄H₂₂P₂ 253.12 253.17 19 cyclopentylMgBr 2.0 M/Ether C₂₀H₃₄P₂337.21 337.31 20 CH₃(CH₂)₉MgBr 1.0 M/Ether C₃₀H₅₈P₂ 481.40 481.57 214-fluoro-3-CH₃—C₆H₃MgBr 10 M/THF C₂₄H₂₈P₂F₂ 417.16 417.27 223,4-difluoro-C₆H₃MgBr 0.5 M/THF C₂₂H₂₂P₂F₄ 425.11 425.23 23p-CH₃(CH₂)₃C₆H₄MgBr 0.5 M/THF C₃₀H₄₂P₂ 465.28 465.19 243-fluoro-2-methyl-C₆H₃MgBr 0.5 M/THF C₂₄H₂₈P₂F₂ 417.16 417.28 252-naphthylMgBr 0.25 M/THF C₃₀H₃₀P₂ 453.18 453.31 26 p-CH₃S—C₆H₄MgBr 0.5M/THF C₂₄H₃₀P₂S₂ 445.13 445.25 27 3-methoxy-C₆H₄MgBr 0.5 M/THFC₂₄H₃₀P₂O₂ 413.17 413.34 28 3-fluoro-4-methyl-C₆H₃MgBr 0.5 M/THFC₂₄H₂₈P₂F₂ 417.16 417.3 29 2-methoxy-C₆H₄MgBr 0.5 M/THF C₂₄H₃₀P₂O₂413.17 413.27 30 4-methoxy-C₆H₄MgBr 0.5 M/THF C₂₄H₃₀P₂O₂ 413.17 413.3231 C₆H₅O—C₆H₄MgBr 0.5 M/THF C₃₄H₃₄P₂O₂ 537.20 537.67 32p-(CH₃)₂NC₆H₄MgBr 0.5 M/THF C₂₆H₃₆P₂N₂ 439.23 439.37 332,4-difluoro-C₆H₃MgBr 0.5 M/THF C₂₂H₂₂P₂F₄ 425.11 425.24 342,4,6-trimethyl-C₆H₂MgBr 1.0 M/THF C₂₈H₃₈P₂ 437.24 437.41 35H₂C═C(CH₃)MgBr 0.5 M/THF C₁₆H₂₆P₂ 281.15 281.21 38 CH₂═CHCH₂MgCl 1.0M/Ether C₁₆H₂₆P₂ 281.15 281.23 39 (CH₃)₃SiCH₂MgCl 1.0 M/EtherC₁₈H₃₈P₂Si₂ 373.20 373.31 40

0.5 M/THF C₂₂H₃₈P₂O₄ 429.22 429.29

Example 41

[0117]

[0118] A flask was charged with 4.00 g (14.9 mmol) of[2-(tetramethylphospholyl)ethyl]dichlorophosphine and ca. 30 mL oftetrahydrofuran and was cooled to −30° C. To this was added dropwise 15mL of a 1.0 M solution of lithium aluminum hydride in diethyl ether.After warming to room temperature, tetrahydrofuran was removed in vacuo,and the product was extracted with hexane and filtered. Removal ofhexane in vacuo produced the oily compound[2-(tetra-methylphosphoyl)ethyl]phosphine. ³¹P NMR (122 MHz,tetrahydrofuran-d₈): δ 17 (s),-128 (t, J(P-H)=190 Hz). This crudeproduct was not purified further. In another flask, 1.30 g of thisproduct (6.49 mmol) was dissolved in 80 mL of tetrahydrofuran, and 5.1mL of 1.6 M n-butyllithium (8.2 mmol) was added to the flask at roomtemperature and this was stirred for one hour. To this was addeddropwise 1.50 g of 2,7-dimethyl-(R,R)-3,6-decadiylsulfate dissolved in 8mL of THF. This was stirred for 1.5 h at room temperature. Then, 5.1 mLof 1.6 M n-butyllithium (8.2 mmol) was added to the flask at roomtemperature and this was stirred for one hour. The reaction mixture wasquenched with 3 mL of methanol, and the solvent was removed in vacuo.The product was extracted with 150 mL of pentane, and was filtered.Removal of pentane in vacuo yielded 1.74 g of[2-(tetramethylphospholyl)ethyl]-[(R,R)-2,7-dimethyl-3,6-decadiyl]phosphinewhich was purified by oil sublimation (160° C., ca. 1 torr). ³¹P{¹H} NMR(122 MHz, C₆D₆): δ 18 (s), -9 (s).

Example 42 Olefin/Carbon Monoxide Copolymerization Using DiphospholeCoordinated Palladium Catalysts

[0119] Synthesis of [1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMeCl

[0120] The solution of 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane(1.538 g, 5.019 mmol) and (COD)PdMeCl(1.267 g, 4.780 mmol) in 60 mLCH₂Cl₂ was allowed to stir for 1.5 hr at RT. The mixture was filtered.The filtrate was concentrated to ca. 10 mL, followed by addition of 160mL pentane. The solid was filtered, washed with 3×10 mL pentane anddried in vacuo. Milky white product (2.128 g, 96%) was obtained. ¹HNMR(CD₂Cl₂): δ 0.27(dd, 3H, Pd-CH₃); 1.80-2.14 (m, 28H, overlappedligand CH₂'s and CH₃'s). ³¹P NMR(CD₂Cl₂): δ 59.63, 73.55 (1P each).

Example 43 Synthesis of{[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMe(CH₃CN)} SbF₆

[0121] To a −30° C. solution of[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMeCl (1.47 g, 3.17mmol) and CH₃CN (1.30 g, 31.7 mmol) in 50 mL CH₂Cl₂ was added AgSbF₆(1.090 g, 3.17 mmol). This was allowed to warm up slowly to RT and stirat RT for 30 min. The mixture was filtered. The filtrate wasconcentrated to ca. 5 mL. To the concentrated solution was added 80 mLpentane. The solid was filtered, washed with 3×10 mL pentane and driedin vacuo. Yellow solid (2.172 g, 97%) was obtained. ¹H NMR(CD₂Cl₂): δ0.29(dd, 3H, Pd-CH₃); 1.80-2.20 (m, 28H, overlapped ligand CH₂'s andCH₃'s); 2.24(s, 3H CH₃CN). ³¹P NMR(CD₂Cl₂): δ 60.62, 73.32(d, J=18.0 Hz,1P each).

Example 44 Synthesis of[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl

[0122] The solution of1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethyl-hydrazine (0.341 g,1.01 mmol) and (COD)PdMeCl (0.224 g, 0.845 mmol) in 20 mL CH₂Cl₂ wasallowed to stir for 1.5 hr at RT. The mixture was filtered. The filtratewas concentrated to ca. 5 mL, followed by addition of 75 mL pentane. Thesolid was filtered, washed with 3×5 mL pentane and dried in vacuo. Redbrown product (0.253 g, 61%) was obtained. ¹H NMR(CD₂Cl₂): δ 0.25 (dd,3H, Pd-CH₃); 1.98 (s, 12H, 3,4-CH₃'s); 2.01 (dd, 12H, 2,5-CH₃'s); 2.56(d, J=8.4 Hz, 3H, N—CH₃); 2.64 (d, J=10.2 Hz, 3H, N—CH'₃). ³¹PNMR(CD₂Cl₂): δ 115.80 (d, J=30.3 Hz, 1P); 127.40 (d, J=28.9 Hz, 1P).

Example 45 Synthesis of{[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)}SbF₆

[0123] To a −30° C. solution of[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl(0.20 g, 0.406 mmol) and CH₃CN (0.17 g, 4.15 mmol) in 20 mL CH₂Cl₂ wasadded AgSbF₆ (0.1394 g, 0.406 mmol). This was allowed to warm up slowlyto RT and stir at RT for 40 min. The mixture was filtered throughCelite® filteration aid. The filtrate was concentrated to ca. 5 mL. Tothe concentrated solution was added 75 mL pentane. The solid wasfiltered, washed with 2×5 mL pentane and dried in vacuo. Light brownsolid (0.23 g, 77%) was obtained. ¹H NMR(CD₂Cl₂): δ 0.27 (dd, 3H,Pd-CH₃); 1.87 (s, 12H, 3,4-CH₃'s); 1.88 (dd, 12H, 2,5-CH₃'s); 2.26 (s,3H CH₃CN); 2.57 (d, J=8.7 Hz, 3H, N—CH₃); 2.67 (d, J=11.1 Hz, 3H,N—CH'₃). ³¹P NMR(CD₂Cl₂): δ 115.58 (d, J=28.5 Hz, 1P); 125.48 (d, J=30.3Hz, 1P).

Polymerizations

[0124] Reactions were done by using either well-defined palladiumcatalysts such as [(diphosphole)PdMe(CH₃CN)]SbF₆ or catalysts generatedin situ by mixing the diphosphole ligand with the palladium salts suchas [Pd(CH₃CN)₄](BF₄)₂ or Pd(OAc)₂. Adding strong acid such asp-toluenesulfonic acid is important when Pd(OAc)₂ is used as thecatalyst precursor. Adding excess of benzoquinone as the oxidant ingeneral helps the copolymer yield. The copolymerization works in commonorganic solvents such as CH₂Cl₂, chlorobenzene and methanol. Thesynthesis of the organometallic complexes were carried out in a nitrogendrybox. Catalyst screening was more conveniently done in multishakertubes. When using shaker tubes for ligand and catalyst scouting (Table2), 25 mL-sized tubes were used. Ligand, catalyst precursor (orsingle-component catalyst), oxidant (sometimes also p-CH₃C₆H₄SO₃H.H₂Oacid) and 5 mL of specified solvent(s) were mixed in the shaker tubes.After purging with nitrogen, these tubes were pressured up withethylene/CO (1:1) mixed gas and was shaken at 60° C. under ethylene/COpressure for 18 hr.

Example 46 High Pressure slurry ECO Copolymerization (100° C., 900 psi)

[0125] {[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMe(CH₃CN)}SbF₆(1.00 g, 1.42 mmole), benzoquinone (3.07 g, 28.4 mmole) and 1460 mLmethanol were charged into an one gallon autoclave. The reactor was thencharged with mixed ethylene/carbon monoxide gas (1:1) and thetemperature was raised up to 100° C. The mixture was allowed to stir at100° C. under 900 psi of E/CO mixed gas for 6 hr. The reaction wasexothermic(cooling coil was used to control the temperature by usingwater as coolant). Upon cooling, the polymer/methanol mixture wastransferred to a blender and was blended to powders. The powdery polymerwas then filtered, washed with methanol repeatedly and dried in vacuo at100° C. for 3 days. White powdery polymer (356 g) was obtained. Based on¹H and ¹³C NMR, the polymer is perfectly alternating ethylene/COcopolymer. The copolymer exhibited a m.p. of 250° C. based on DSC. GPC(HFIP, polyethylene terephthalate standard): Mw=236,000; Mn=46,800;Mw/Mn=5.0.

Example 47 Slurry ECO Copolymerization (60° C., 700 psi)

[0126] {[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMe(CH₃CN)}SbF₆(0.60 g, 0.852 mmole), benzoquinone (4.6 g, 42.6 mmole), 1000 mLmethanol and 500 mL toluene were charged into an one gallon autoclave.The reactor was then charged with mixed ethylene/carbon monoxide gas(1:1) and the temperature was raised up to 60° C. The mixture wasallowed to stir at 60° C. under 700 psi of ECO mixed gas for 6 hr. Thereaction was exothermic (cooling coil was used to control thetemperature by using water as coolant). Upon cooling, thepolymer/methanol mixture was transferred to a blender and was blended topowders. The powdery polymer was then filtered, washed with methanolrepeatedly and dried in vacuo at 100° C. for one day. White powderypolymer (243 g) was obtained. Based on ¹H and ¹³C NMR, the polymer isperfectly alternating ethylene/CO copolymer. The copolymer exhibited am.p. of 242° C. based on DSC. GPC (HFIP, polyethylene terephthalatestandard): Mw=149,000; Mn=63,000; Mw/Mn=2.4.

Examples 48-53 Shaker Tube screening of Ligands and Catalysts for ECOCopolymerization (60° C., 18 hr)

[0127] TABLE 1 Shaker tube experiments for Ethylene/CO copolymerizationCatalyst or Benzo- E/CO Ligand precursor quinone Acid Pressure Copolymerm.p Ex. mg (mg) (mg) (mg) Solvent (psi) Mw/Mn Yield (g) (° C.) 48 0 C-1(4.7) 14.4 0 CH₃OH 708 na 8.5 na 49 0 C-1 (42) 0 0 CH₃OH 880 na 23.3 na50 L-1 Pd(OAc)₂ 130 228 CH₃OH/ 800 na 0.5 na (22) (12.5) toluene 2:1 510 C-1 (2.0) 6.3 0 CH₃OH 885 381,000/ 1.53 253 151,000 52 0 C-2 (29.4)89.6 0 CH₃OH 885 509,000/ 5.0 245 218,000 53 L-2 P-1 (5.7) 27.6 0 CH₃OH600 707,000/ 11.8 na (5.5) 312,000

Example 54 ATRP of MMA Using Cu(1)-diphosphole Complex as Catalyst

[0128] MMA was passed through a basic alumina column to removeinhibitor, then degassed by freeze-thaw cycle three times. 10 mg of CuCland 62 mg of 1,2-bis(2,3,4,5-tetramethylphospholyl) ethane were put into5.0 mL of degassed toluene. 5.0 mL of purified MMA and 66 μL of2,2′-dichloroacetophenone were added into the above catalyst solution.The solution was mixed well in a Schlenck flask and the flask was sealedunder nitrogen and then immersed in an oil bath set at 80° C.Polymerization proceeded at 80° C. with stirring for 16 hrs. Afterpolymerization was stopped, the solution was diluted with more tolueneand then polymer was precipitated into methanol. Polymer solid wascollected by filtration, washed with methanol, and dried under vacuum.0.35 g polymer was obtained (7.5% conversion of MMA). The polymer wasanalyzed by GPC with THF as eluent and PMMA as standard. The numberaverage molecular weight (M_(n)) was 20200 and M_(w)/M_(n) was 1.32.

We claim:
 1. A process for preparing compounds of formulae I and II

comprising reacting suitable equivalents of a compound of formulaX₂P-A-PX₂ (¹H) with a compound of formula IV;

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₂ andR₃ together can optionally form a ring; Cp is cyclopentadienyl; X isselected from the group consisting of Cl, Br, and I; A is a divalentgroup consisting of optionally-substituted chains of from 1 to 12linear, branched, or cyclic carbons, optionally containing one or moreheteroatoms or organometallic groups in the chain, and —N(R₇)—N(R₈)—;and R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.
 2. The process ofclaim 1 where A is selected from the group consisting of a carbon chainof 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independentlyselected from the group consisting of hydrogen, hydrocarbyl, andsubstituted hydrocarbyl.
 3. The process of claim 2 where R₁, R₂, R₃, andR₄ are alkyl groups.
 4. The process of claim 1 wherein the compound offormulae I or II is selected from the group consisting of1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane;1,2-bis(2,3,4,5-tetraethylphospholyl)ethane;1,1-bis(2,3,4,5-tetramethylphospholyl)methane;1,1-bis(2,3,4,5-tetraethylphospholyl)methane;1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine,1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane; and1-(2,3,4,5-tetra-methylphospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine.5. A compound of the formula

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; Cp iscyclopentadienyl (η⁵—C₅H₅); A is a divalent group consisting ofoptionally-substituted chains of from 1 to 12 linear, branched, orcyclic carbons, optionally containing one or more heteroatoms ororganometallic groups in the chain, and —N(R₇)—N(R₈)—; and R₇ and R₈ areindependently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.
 6. The compound of claim 5where A is selected from the group consisting of a carbon chain of 1-3carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈ are independently selectedfrom the group consisting of hydrogen, hydrocarbyl, and substitutedhydrocarbyl.
 7. The compound of claim 6 wherein R₁, R₂, R₃, and R₄ arealkyl groups.
 8. The compound of claim 7 wherein R₅ and R₆ are selectedfrom the group consisting of alkyl groups and Cl.
 9. The compound ofclaim 8 that is1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dichlorophosphinoethane-1,2-dimethylhydrazine;[2-(tetramethylphospholyl)ethyl]-[(R,R)-2,7-dimethyl-3,6-decadiyl]phosphine;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-chlorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-tert-butylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diethynylphosphinoethane,1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-propynyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(phenylethynyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-divinylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-dicyclopentylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(n-decyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-fluoro-3-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-butylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-2-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-naphthyl) phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methyl-thiophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-methoxyphenyl)phosphinoethane,1-(2,3,4,5-tetramethylphospholyl)-2-di-(3-fluoro-4-methylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-methoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(4-phenoxyphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-[4-(dimethylamino)phenyl]phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4-difluorophenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-(2,4,6-trimethylphenyl)phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-isopropenylphosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-diallyl-phosphinoethane;1-(2,3,4,5-tetramethylphospholyl)-2-di-trimethylsilylmethyl-phosphinoethane;and1-(2,3,4,5-tetramethylphospholyl)-2-di-[2-[1,3]dioxan-2-yl-ethyl]phosphinoethane.10. A coordination compound comprising one or more transition metalscomplexed to one or more of the following compounds as ligands

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. 11.The coordination compound of claim 10 wherein the transition metal isPd.
 12. The coordination compound of claim 11 wherein A is selected fromthe group consisting of a carbon chain of 1-3 carbons and —N(R₇)—N(R₈)—,and wherein R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. 13.The coordination compound of claim 12 wherein R₁, R₂, R₃, and R₄ arealkyl groups.
 14. The coordination compound of claim 13 wherein R₅ andR₆ are selected from the group consisting of alkyl groups and Cl. 15.The coordination compound of claim 14 that is[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMeCl;{[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMe(CH₃CN)}SbF₆;[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl; or{[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)} SbF₆.
 16. A process for preparing apolyketone comprising contacting a mixture of carbon monoxide with oneor more alkenes under polymerization conditions with a catalystcomprising a transition metal complexed with one or more ligands of theformulae IIA or VA

wherein the rings are optionally-substituted and are optionally membersof a larger bicyclic or tricyclic ring system; each P atom is bonded toonly three other atoms in the ligand; two atoms in the ring adjacent tothe P atom are C atoms; R₅ and R₆ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, Cl,Br, I, N, O, and S; R₅ and R₆ together can optionally form a ring; A isa divalent group consisting of optionally-substituted chains of from 1to 12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. 17.The process of claim 16 wherein the transition metal is Pd.
 18. Theprocess of claim 17 wherein the ligand is of the formulae V or II

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. 19.The process of claim 18 wherein A is selected from the group consistingof a carbon chain of 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈are independently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.
 20. The process of claim 19wherein R₁, R₂, R₃, and R₄ are alkyl groups.
 21. The process of claim 20wherein R₅ and R₆ are selected from the group consisting of alkyl groupsand Cl.
 22. The process of claim 21 wherein the catalyst is[1,2-bis(2,3,4,5-tetramethylphospholyl)ethane]PdMeCl;{[1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane]PdMe(CH₃CN)} SbF₆;[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMeCl; or{[1,2-bis(2,3,4,5-tetramethylphospholyl)-1,2-dimethylhydrazine]PdMe(CH₃CN)}SbF₆.
 23. The process of claim 17 wherein the catalyst is prepared insitu from 1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane and Pd(OAc)₂, orfrom 1,2-bis(2,3,4,5-tetraethylphospholyl)-propane and[Pd(CH₃CN)₄]BF₄)₂.
 24. The process of claim 16 wherein the alkene isethylene.
 25. A process for polymerizing an acrylic monomer comprisingcontacting at least one acrylic monomer under polymerization conditionswith a catalyst comprising Cu(I) complexed with one or more ligands ofthe formulae IIA or VA

wherein the rings are optionally-substituted and are optionally membersof a larger bicyclic or tricyclic ring system; each P atom is bonded toonly three other atoms in the ligand; the two atoms in the ring adjacentto the P atom are C atoms; R₅ and R₆ are independently selected from thegroup consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, Cl,Br, I, N, O, and S; R₅ and R₆ together can optionally form a ring; A isa divalent group of optionally-substituted chains of from 1 to 12linear, branched, or cyclic carbons, optionally containing one or moreheteroatoms or organometallic groups in the chain, and —N(R₇)—N(R₈)—;and R₇ and R₈ are independently selected from the group consisting ofhydrogen, hydrocarbyl, and substituted hydrocarbyl.
 26. The process ofclaim 25 wherein the ligand is of the formulae V or II

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl; R₅ andR₆ are independently selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, Cl, Br, I, N, O, and S; R₂ and R₃together and R₅ and R₆ together can optionally form a ring; A is adivalent group consisting of optionally-substituted chains of from 1 to12 linear, branched, or cyclic carbons, optionally containing one ormore heteroatoms or organometallic groups in the chain, and—N(R₇)—N(R₈)—; and R₇ and R₈ are independently selected from the groupconsisting of hydrogen, hydrocarbyl, and substituted hydrocarbyl. 27.The process of claim 26 wherein A is selected from the group consistingof a carbon chain of 1-3 carbons and —N(R₇)—N(R₈)—, wherein R₇ and R₈are independently selected from the group consisting of hydrogen,hydrocarbyl, and substituted hydrocarbyl.
 28. The process of claim 27wherein R₁, R₂, R₃, and R₄ are alkyl groups.
 29. The complex of claim 28wherein R₅ and R₆ are selected from the group consisting of alkyl groupsand Cl.
 30. The process of claim 25 wherein the acrylic monomer ismethyl-methacrylate.
 31. The process of claim 25 wherein the catalyst ispreapred in situ from 1,2-bis(2,3,4,5-tetramethylphospholyl)-ethane andCuCl.